Production of high octane fuel components



June 16, 1953 J. P. HOGAN 2,642,467

PRODUCTION OF HIGH OCTANE FUEL COMPONENTS Filed May 11, 1950REGENERATION GAs 4.9

FEED o f as I 43 t 53 4 56 52 63 sPENT 45 571 REGENERATION GAS\ 6O 66 e568 58 59 REGENERATION GAs I 22 FEE 26 D FEED Io l7 24 I6 l I2 70 II I 79I8 25 PROOuGT I 2| I9 28 I 21 PRODUCT 23 t SPENT I REGENERATION GAS F/G.82

F IG. 3.

' INVENTOR.

J. P. HOGAN MFW A 7'7'ORNEYS Patented June 16, 1953 PRODUCTION OF HIGH.OGTANE FUEL- GOMPONENTS John Paul Hogan, Bartlesville; k-la.,assign'o'rto Phillips Petroleum Company; a corporation of DelawareApplication May 11,1950, Serial No. 161,391

13 Claims. (Cl. 260-68315) This invention relates. to an improvedprocess forthe production of 'highyields of 2',2,3-trimeth= ylpentene'('methyltriptene). specificaspects it relates to animproved method for.producing 2,2,3-trimethylpentene by' con trolled copolymerization ofZ-butene and isobutene. In one specific embodiment my invention relatesto the production of a high octane gasoline component polymer containing2,2,3-

trimethylpentene.

Numerous methods are disclosed in the'art for the polymerization orcopolymerization of ole-.

fins. Various catalysts have been disclosed such as sulfuric. acid,phosphoric acid, silica-alumina, activated natural clays, and the like.In the processes disclosedattempts have been made'to improve. theyields.or quality of the product. In

mostcases, however, either yieldor quality has beensacrificed.

An object of this invention is to' provide an improved process for thecopolymerization of 2- butene with isobutene.

Another object is to provide an improved" method for producing2,2,3-trimethylpentene in continued high yields.

Another objectis, in the process for, produc-'- ing.2,2,3-trimethylpenten'e by copolymerization.

of. Z-butene and isobutene, to suppress the formation of undesirabledifiicultly separated 3,4-di methylhexene.

Another object is to reduce the proportion of 2,2,4-trimethylpentene. inrelation to the propor-.

tionof 2,2,3-trimethylpentene produced by the copolymerizationofZ-butene With isobutene.

Another object is to produce by the copolymerization of 2-butene withisobutene a, Caproduct" at-allconditions of catalyst activity whichwhen'hydrogenated is of more uniform high octane rating.

Various other objects and advantages of my invention will be apparent toone skilled in the art. from the following discussion. and disclosure.

1 have. discovered an improvement in the method. for thecopolymerization. of Z-butene' tainingcobalt oxide instead. of'ni'ckeloxide as disclosed in. copending: application Serial No; 169,848,identified above; I nickel'oxide'catalyst used isiully set out in Pat-In'. one. of its more Preparation of. the" decomposable to alumina uponheating.

ent Nol 2,606,940. According to the teaching ofthis'patent a preferredmethod of preparing the" catalyst istoimpregnate silica gel with anaqueous solution of'an aluminum salt which is Such salts are the sulfateand nitrate of aluminum. The thus prepared silica-alumina is thenimpregnated with an aqueous solution of nickel nitrate which issubsequently converted to the oxide by heating. This catalyst is thenactivated by heating in an oxygen containing atmosphere atatemperaturewithin the range of '300 to '700" C. More complete details andmodifications of the catalyst preparation are found in this patent underthe headings Preparation of Catalyst, Percentage of Nickel Oxide, andUse of Alumina as'Promoter, and by referring to Ex-. amples 3 and 5; Thecobalt oxide catalyst is prepared in the same manner;

I have found that during the'polymerization cycle the proportion of2,2,3-trimethylpentene in the polymerprod'uced decreases with increasedtime on'stream. Thus, I have found that, when reaction conditions are inall other respects maintained". constant, as the catalyst ages theproportion of 2,2,3-trimethylpentene in the Ca fraction decreases andtheproportion of 2,2,4- trimethylpentene increases. Since the 2,2,3-triinethylpentene on hydrogenation is of better octane numberand'has abetter'rich mixture performance than the 2,2,4-isomer, it is desirableto'maintain the proportion of the former at a maxim'um'andthe latter ata minimum.

Inaccordancewith my" invention, the proportion of 2,2,3-trimethylpentene produced by the copolymerization of 2-butene withisobutene in the-presence of a silica-alumina catalyst promotedwitha'materi'al such as nickel or cobalt oxide can'b maintained at a uniformhigh level and the proportion of 2,2,4-trimethylpentene maintained at alow'level by controlling the ratio of Z-but'ene' to'i'sobutenein thehydrocarbon feed in accordance with theage of the catalyst. Thus, withnew catalyst or with freshly regenerated catalyst; optimum production of2,2,3-trimethylpentene and minimum" production of2,2,4-trimethylpentenecan be'obtainedwith a feed containihg arelativelylower ratio of 2'-butene to isobutene, while later on in thecycle similar proportionsof2,2,3'-ti*imethy1pentene and2,2,4-trimethylpentene areproduced only with an increased ratio ofZ-bu'tene to isobutene. More specifically,

I have foundth'at in the production of copolymer from the reaction ofZ-butene' withisobutene it i's'desirableto'change the ratio of Z-butene"todso'buten'e from themangeof 5 :1- to 14:1 when operation are thefollowing: temperature '75 to ,7

120 F., liquid hourly space velocity 5 to 15, and 1 pressure 5 to 20atmospheres. Operating in these ranges the yield of2,2,3-trimethylpentene in the polymer product is high and the2,2,4-isomer and 3,4-dimethylhexene are low, thus maintaining the octanenumber of the hydrogenated product high.

A more clear understanding of some of the many aspects of my inventionmay be had by referring to the attached drawings, which are schematicflow diagrams of three modifications ofmy p -v ess. Various additionalvalves, pumps,.and other conventional equipment necessary for thepractice of this invention will be familiar to one skilled in the art,and have been omitted for the sake of clarity. The descriptions of thedrawings provide three methods of operating my process. However, whilethey are representative in general of my process, various minor changesmay be made in adapting them to the various conditions within the scopeof the invention.

Refer now to Figure 1, Which is a flow diagram of a continuous process.The mode of operation characterized by this drawing utilizes astationary catalyst bed with alternate on-stream and regenerationperiods. From an economical standpoint it is desirable to utilize twocatalyst chambers as indicated. However, intermittent operation may becarried out with only one catalyst chamber. Two-butene and isobutene inadmixture in previously disclosed ratios are fed through line H] tolines II and I2 through which it is passed to reaction chambers I3 andI4 respectively. In the first step of the operation valve I6 in line II]will remain closed, and valve I! in line II will remain open, therebycausing the feed to pass only to chamber I3. Effluent from chamber I3 isremoved via line I8 and is passed therefrom through line I9 to asuitable separation zone wherein the polymer is recovered and from whichit is passed to a hydrogenation zone. When operating in this mannervalve 20 remains closed and valve 2| remains open.

If chamber I4 has been previously used, regeneration gas is passedthrough line 22 to line I2 and therefrom through the catalyst chamber,regenerating the spent catalyst therein. Spent regeneration gas iswithdrawn from chamber I4 through line 25 and is passed therefromthrough line 23 to suitable exhaust. When so operating, valves 24 and 21remain closed, and valves 26 and 28 remain open.

When chamber I3 becomes impractical to operate because of lost catalystactivity, valve H in,

line II is closed, as is valve 2I in line I9, and valve 24 in line 22and valve 20 in line I8 are opened. At the same time, chamber I4 will beput on-stream by opening valve I6 and allowing feed to pass throughlines II] and I2 into the reaction chamber and by opening valve 21 inline 25. Product from chamber I4 will be withdrawn through line 25 toline I9 and passed to further treatment, such as fractionation andhydrogenation. When product is being recovered through line 25, valve 28in line 23 will be closed.

Refer now to Figure 2, which is similar to Figure 1 in that the catalystis maintained in stationary beds which are regenerated alternately. Afeed stream containing 2-butene and isobutene in the proper proportionsfor fresh catalyst is passed through'line 35 to line 36 with valve 31 inline 35 being closed, and valve 38 in line 36 open. The feed enterschamber 39 and is copolymerized at conditions previously described forfresh catalyst. It has been found that during the first part of thecycle, when the catalyst. is relatively fresh, about equal quantities of2-butene and isobutene are used up. Therefore, effluent from thecatalyst chamber when the catalyst is fresh will contain Z-butene in aratio greater than that of the fresh feed introduced to the chamber. Inview of this, applicant has found it quite desirable to pass theeflluent from a catalyst which is being used for the first cycle througha chamber which has been partially spent. To utilize the catalyst to theutmost, applicant therefore passes an effluent from a first catalystreaction in which the 2-butene is in a higher ratio than in the originalfeed toa catalyst of considerably less activity than that with which thefeed was originally contacted. To carry this out, the effluent from zone39 of Figure 2 is withdrawn via line 41 and is passed through lines 42and 43 to chamber44, j

reaction, is regenerated by contacting it with a suitable gas, such ashot oxygen containing gas, introduced thereto via line 49, and withdrawnvia line 4I and exhausted via line 60. In the first cycle of operation,valves 38, 45, 50, 53, 58,

and 68 remain open, while valves 5I, 52, 54, 55,

9, 3T, 51, 59, BI, 67, and 62 are closed. The cycle is then carried outusing chamber 48 as the first reaction chamber and chamber 39 as thesecond reaction chamber with the effluent from chamber 48 beingtransmitted to chamber 39 through line 63. At the same time, chamber 44will be on regeneration and the regeneration gas exhausted therefrom Vialines 46, 65, and. 69. Similarly, the

third cycle will be chamber 44 as a first chamber 4 and chamber 48. asthe second chamber with chamber 39 on regeneration. The effluent fromzone 44 is passed to zone 48 via line 40. The regeneration gas isexhausted from zone 39 via lines 41, 66, and B0.

A third modification of my invention utilizes a moving catalyst bed ofthe conventional type. In Figure 3 the feed gas containing 2-butene andisobutene is passed through line 19 with fresh catalyst from hopper IIto chamber I2. The catalyst moves downwardly through this chamber and asit passes downwardly becomes more spent. The fresh feed entering at thesame or near the same point as the fresh catalyst contacts the freshcatalyst first utilizing-more of the isobutene, and thereby changing theratio so that the proportion of 2-butene is increased. As this gaspasses downwardly through the catalyst, it contacts the more spentmaterial, but since the gas ratio is changed in the optimum direction,product containing approximately the same quantity of2,2,3-trimethylpentene and the 2,2,4-

isomer will be continually produced. Product from, the polymerizationreaction is removed via 1irrer l3 and. isipa'ssed tosuitable' separationmeans and from there to. hydrogenation. Spent. cata-- lyst'is'rrem'ovedfrom the bottom of chamber I2 as by star valve 14 or othersuitable controlling 6 Eivample- The' followingdata were. obtained. in aseries ofruns. in which a 2-butene-isobutene mixture was passedover asilica-alumina catalyst pro- 'n and 1S earned by any sultable a motedwith approximately five weight per cent such as a gas or mechanicallift, to regeneration f nickel oXide The hydrocarbon feed was main ZoneIn this Z011? Sultable c'ontaclfs tained'. in liquid phasein thereaction chamber, the catalyst, regenerating same. Typifying thisand'wwas harged at" a'rate of 10 liquid volumes. operation, the catalystis" transmitted through pen volume of catalyst per hour The reactionconduit to zone 16, where'it countercurrently 10 temperature wasmaintained at F. Fo11Ow contacts regeneration gas introduced through ingth polymerization Step t polymer was sep line H and withdrawnthroughline 18. Fr m aratedfand.hydrogenated, the analysis shown bethis. zonefreshly generated" cat l'yst is carried ing that of the hydrogenatedproduct'in volume through line 19 back to hopper H, from which it percent.

' 2-Butene/ Hours isr t l i t ne stgeiiam H2,2,'4--IMl 2,2,3.-TMPISA-VDMH 011+ is fdlina suitable manner, as by star valve 8|, The datain the above table demonstrate that into the feed gas in line. 10. Inone method of the advantages of the present invention cannot operationwhich may be utilized, a mechanical be obtained by operating at aconstant mol ratio conveyor may transmit the spent catalyst to the ofZ-butene to isobutene. When the fresh cataregeneration zone, andtherefrom to the storage lyst wasput on-stream. at a Z-butene toisohopper. In an alternative mode of operation, a butene. ratio of 10:1the initial production of suitable. carrier gas, such as air or othergas inert 2,2,3-trimethylpentene is high. After 8 hours at to thecatalyst, may be used'to blow the catalyst this ratio, however, theyield of 2,2,3-trimethylfrom the bottom of chamber 12 to theregenerapentene had decreased with an increase in the tion zone, andtherefrom to the catalyst hopper. yield of 2,2,4-trimethylpentene, aless desired Inthismodeofloperationthe gasisintroduced material. In.the-second run the ratio of 2- to the spent catalyst through line 82.When but'ene to isobutene was maintained at 20:1. and using agas inthem-anner-described, separation the yield of 2,2,3.-trimethylpentenefrom this run means .must be provided, allowing th catalyst wasvdesirably high. However, the yieldof 3,4- to drop out from the carriergas. This may dimethylhexene at. this ratio was twice as high merely bethe. expanded area of the upper poras at the. 10:1 ratio. SinceSA-dimethylhexene, tion. of the storage. chamber, or it. may. be awhenhydrogenated to the hexane, has an ASTM cyclone separator or thelike. When the upper octane'rating of only 84, it is desirable tomainportion of thecatalyst hopper is used for this tain. the volume. ofthis material as loW as pospurpose a vent for thelcarrier gas, such asvent sible. After 4 to 8 hours on-stream at a20z1ratio- 83, should beprovided. the yield of 3,4.-dimethylhexene had decreased to Thehydrogenation of the copolymer is strictly almost the same valueproduced at a 10:1 ratio a conventional procedure, and may use anysuitwith fresh catalyst; the yield of 2,2,3-trime'thylable hydrogenationcatalyst and reaction condipentenewas. still high; and the yield of2,2,4- tions which. will provide non-destructivehydrotrimethylpentenewas of the same order of. maggenating. Catalystsuch as nickel oxide-onnitude' asthe yieldata 10:1 ratio with freshkieselguhr, oxides or sulfidesof 6th. group metals,v catalyst. Thus, itis clear that. operation. at a such. as molybdenum and tungsten, eithersupconstant..20.:1 ratiowill. not produce the results ported orunsupported, etc. aresatisfactory. One. taught by the present invention.either. If, howparticularlyadvanatageous catalyst which. may ever,operation using fresh catalyst is begun at a be used is disclosed in U.S. Patent 2,377,411 to 2-butene. to isobutene ratio of about 8:1 to 14:1Frey, issued June 5, 1945. Suitable pressures for andincreased to about18:1 to 25:1, by the time hydrogenation are in the range of 50 to 3,000the catalyst has been on-stream 3 to 6 hours a p. s. i., whiletemperatures are generally in the high yield. of 2,2,3-trimethylpenteneis mainrange of say 100 to 750 F. Contact times and tained, the yieldsof 3,4-dimethylhexene and temperatures and pressures will. varygenerally 2,2,4-trimethylpentene are not inordinately high, within theranges disclosed and selection of suitand. the product on hydrogenationis of uniform able conditions of operation from these ranges high-octanerating. iswell within the skill of the art. In most cases In thepractice of my inventionthe actual onit is desirable to use a highcirculation of hystreanrtime. for the catalyst will depend on drogen,generally above the quantity required whether theolefin feedcontainsimpurities that t t rat -th polymer. Th quantities of hydeposit ascarbonaceous matter or as sulfur drogen used may also be readilyselected by one compounds on. the. catalyst. A high purityfeed skilledin the art. obviously allows longer on-stream periods. The followingspecific example is submitted Although this process has been describedand herewith to show the advantage ofmy process 7 exemplified-in termsof its preferred modificaas applied to the copolymerization of Z-butenetions, it is understood that various changes may withlsobutene. Thereactants andtheir proporbe. made Without departing fromthe spirit andtions and other specific ingredients are presented scope of thedisclosure and of the claims. as beingtypicaland shouldnot beconstrued'lto' l'claimz limit'theinventionundul'y; I. A process for theproduction of'hyd'rocarbons hydrogenatable to high octane rating fuelcomponents which comprises polymerizing 2,- butene with isobutene in amol ratio in the range of :1 to 14:1 in contact with a silica-aluminacatalyst promoted with an oxide of the group nickel oxide and cobaltoxide, continuing the polymerization until the activity of the catalystand yield of polymer have appreciably decreased, thereafter increasingthe mol ratio of Z-butene to isobutene to the range of 18:1 to 25:1 andcontinuing the reaction until catalyst deactivation renders furthercontacting uneconomical, and recovering polymer desirable forhydrogenation.

2. The process of claim 1 utilizing nickel oxide as a promoter.

3. The process. of claiml utilizing cobalt oxide as a promoter.

4. A process for the productionof a polymer having on hydrogenation ahigh octane number and high rich mixture performance as an engine fuelconstituent containing a minimum of low-octane materials which comprisescopolymerizing a mixture of 2-butene and isobutene in the presence of anickel oxide promoted silicaalumina catalyst, initiating saidcopolymerization with said Z-butene and said isobutene being in a molratio to each other in the range of 5:1 to 14:1, continuing saidcopolymerization for a period of 3 to 6 hours, thereafter increasing theratio of 2-butene to isobutene to within the range of 18:1 to 25 1, andcontinuing the polymerization at the higher ratio until furthersubstantial deactivation of the catalyst is effected, and separating andrecovering the C8 polymer from the effluent of said copolymerization.

5. A process according to claim 4 wherein said copolymerization iscarried out in liquid phase.

6. A process for the production of maximum quantities of2,2,3-trimethylpentene in the re-v sultant polymer product from thecopolymerization of 2-butene with isobutene and a reduction in quantityof materials which when hydrogenated have a lower octane rating and richmixture performance than hydrogenated 2,2,3-trimethylpentene, whichcomprises contacting in liquid phase a mixture of Z-butene and isobutenein a mol ratio in the range of 8:1 to 14:1 with a nickel oxide promotedsilica-alumina catalyst at a temperature in the range of 30 to 200 F., apressure in the range of 1 to 50 atmospheres, and a liquid hourly spacevelocity in the range'of 1 to 20, continuing the contacting at the sameconditions of reaction for a period in the range of 3 to 6 hours atwhich time the ratio of 2-butene to isobutene is increased to within therange of 18:1 to 25:1, continuing the reaction until uneconomicalbecause of catalyst deactivation, and recovering a Cl; polymer fractionfrom the effluent of said reaction which on hydrogenation hasexceptionally high octane number and rich mixture performance.

7. A process for the production of a C8 hydrocarbon polymer containing amaximum of 2,2,3- trimethylpentene and a minimum of2,2,4-trimethylpentene and 3,4-dimethy1hexene which comprises contactinga mixture of Z-butene and isobutene in a mol ratio in the range of 8:1to14:1 and in liquid phase with a silica-alumina catalyst promoted with0.05 to weight per cent nickel oxide, carrying out the contacting at atemperature in the range of 75 to 120 F., a pressure in the range of 5to 20 atmospheres, and a liquid hourly space velocity in the range of 5to 15, continuing the contacting at the same conditions of reaction fora period in the range to isobutene is increased to within the range of18:1 to 25:1, and recovering a Ca hydrocarbon polymer from the efiiuentof the reaction.

8. A, process according to claim 7 wherein the catalyst is promoted with5 per cent of nickel oxide, the first ratio of 2-butene to isobutene is10:1, and the second ratio of 2-butene to isobuteneis changed after 4hours to 20:1.

9. A continuous process for the production of C9 hydrocarbon polymer ofhigh octane rating and high rich mixture performance which comprisesintroducing amixture of 2-butene and isobutene in a ratio in the rangeof 5:1 to 14:1 to a first reaction zone containing a silica-aluminacatalyst promoted with nickel oxide, reacting the components of saidmixture for a period of time E in the range of 3 to 6 hours, thereafterincreasing the ratio of 2-butene to isobutene to within the range of18:1 to 25:1 and continuing the reaction: at the increased ratio untiluneconomical because of catalyst deactivation, at this point shiftingthe feed to a reaction zone containing fresh catalyst and changing theratio of 2-butene to isobutene in the feed to 5:1 to 14:1, continuingfirst ratio of 2-butene to isobutene is 10:1 and the second ratio is20:1.

11. A continuous process for the production of Ca hydrocarbon polymer ofexceptionally high octane rating and rich mixture performance whichcomprises contacting a mixture of 2-butene and isobutene in a ratio of5:1 to 14:1 with a silica-alumina catalyst promoted with 0.01 to 10weight per cent nickel oxide calculated as nickel for a period of 3 to 6hours in a first catalyst zone, passing the efiiuent from this zone in,

which the ratio of Z-butene to isobutene has been increased by thepolymerization reaction to a second catalyst zone previously used for aperiod of 3 to 6 hours to polymerize 2-butene and isobutene in a ratioof 5:1 to 14:1, and continuing the polymerization until the catalyst hasbecome deactivated, concomitantly regenerating the catalyst in a thirdzone which has been used previously for both production steps of thecycle, shifting the fresh feed from the first catalyst zone to theregenerated third catalyst zone and passing the efiiuent from this zonethrough the first catalyst zone, concomitantly regenerating the secondcatalyst zone, after 3 to 6 hours shifting the fresh feed fromthe thirdcatalyst zone to the second catalyst zone and passing the efiiuent fromthis zone to the third catalyst zone while concomitantly regeneratingthe first catalyst zone, and continuously carrying out the cycledescribed while recovering a Ca hydrocarbon polymer from thepolymerization efiiuent and passing the C8 polymer to a hydrogenationzone wherein it is converted into high octane rating and rich mixtureperformance motor fuel constituents.

12. A process according to claim 11 wherein the polymerization reactionconditions are a temperature in the range of 30 to 200 F., a pressure inthe range of 1 to 50 atmospheres, and a liquid hourly space velocity inthe range of 1 to 20.

13. A continuous process for the production of C8 hydrocarbon polymer ofexceptionally high octane rating and rich mixture performance whichcomprises passing a mixture of 2-butene and isobutene in a ratio of 5:1to 14:1 in concurrent contact under polymerizing conditions with acontinuously downwardly moving bed of freshly regenerated silica-aluminacatalyst promoted with nickel oxide at a temperature in the range of 30to 200 F., a pressure in the range of 1 to 50 atmospheres, and a liquidhourly space velocity in the range of 1 to 20, so that as thepolymerization proceeds the ratio of 2-butene to isobutene progressivelyincreases and the reactants are progressively contacted with less activecatalyst thereby maintaining a substantially uniform yield of Capolymer, withdrawing spent catalyst from the bottom of said moving bedof catalyst and passing same to regeneration, regenerating said spentcatalyst and returning same to the top of said moving bed, removingeffluent from said contacting near the bottom of said moving bed ofcatalyst and recovering therefrom a Ca polymer fraction, hydrogenatingsaid Cs polymer and recovering from said hydrogenation motor fuelcomponents of high octane rating and rich mixture performance.

JOHN PAUL HOGAN.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 2,368,110 Buell Jan. 30, 1945 2,377,411 Frey June 5, 19452,470,171 Kennedy et a1. May 17, 1949

1. A PROCESS FOR THE PRODUCTION OF HYDROCARBONS HYDROGENATABLE TO HIGHOCTANE RATING FUEL COMPONENTS WHICH COMPRISES POLYMERIZING 2BUTENE WITHISOBUTENE IN A MOL RATIO IN THE RANGE OF 5:1 TO 14:1 IN CONTACT WITH ASILICA-ALUMINA CATALYST PROMOTED WITH AN OXIDE OF THE GROUP NICKEL OXIDEAND COBALT OXIDE, CONTINUING THE POLYMERIZATION UNTIL THE ACTIVITY OFTHE CATALYST AND